Vinyl ethyl ether or thioether sulfones



United States Patent 011cc 3,517,068 VINYL ETHYL ETHER R THIOETHERSULFONES Albert C. Perrin-o, Cranston, R.I., assignor to I.C.I./0r-

gszinicg/lne, Providence, R.I., a corporation of Rhode an No Drawing.Original application May 1, 1963, Ser. No. 277,129. Divided and thisapplication Sept. 11, 1967, Ser. No. 674,038

Int. Cl. C07c 147/04; D06m 13/ 32, 13/38 US. Cl. 260-607 8 ClaimsABSTRACT OF THE DISCLOSURE A vinyl ethyl sulfone having one of theformulae:

R0 R0 R0 R0 R X BH H s.o EH in which R is hydrogen, R is a member of thegroup consisting of straight-chain alkyl groups having -18 carbon atoms,branched alkyl groups having 10-16 carbon atoms and alkyl phenyl groupsin which the alkyl group has 9-12 carbon atoms, and X is a member of thegroup consisting of oxygen and sulfur. The compounds are useful intreating cellulosic textiles to render them permanently water repellentand resistant to water-borne stains and to provide a soft, pleasinghand.

This is a division of my copending application, Ser. No. 277,129, filedMay 1, 1963.

The present invention relates to new hydrophobic vinyl sulfonederivatives and related latent vinyl sulfone deriva tives, and to theiruse in the treatment of textiles. They are particularly useful fortreating cellulosic textiles to render them permanently water repellentand resistant to water-borne stains and to provide a soft, pleasinghand. These treatments are effected in such a way that a treating agentis bonded to the textile by a primary chemical bond and is not removedby laundering, dry-cleaning and similar operations during normal use.

The new vinyl sulfone derivatives are vinyl-ethyl sulfones in which theethyl group is substituted in the beta position with an oxygen, sulfuror nitrogen and have one of the formulae:

R0 R0 R0 R-X--CHGHSO2C=CHR0 and R1 R0 R0 R0 N-( JH-JJHSOziJ=CHRo R2 inwhich R is hydrogen or methyl, R is a straight-chain saturated orunsaturated alkyl group having 10-18 carbon atoms, a branched alkylgroup containing 10-16 carbon atoms or an alkylaryl group such as analkyl phenyl group in which the alkyl group has a straight chain or isbranched and contains 9-12 carbon atoms.

R is a saturated or unsaturated straight-chain alkyl group containing10-18 carbon atoms.

R is a saturated or unsaturated straight-chain alkyl group containingl-18 carbon atoms.

X is oxygen or sulfur. Latent vinyl sulfones within the scope of theinvention have the following formulae:

where R and X are the same as previously described, R -=I-I or methyland A is a good leaving group for E elimination. More specifically, Arefers to three general classes:

Patented June 23, 1970 (l) X is O and A is the cation of weak nitrogenbases, i.e.,

A=ii z R5 R4 where R R and R are alkyl, aryl or alkaryl groups of atertiary amine having an ionization constant less than 10- and Z is ananion such as chloride, bromide, iodide, sulfate, alkyl sulafte,nitrate, benzenesulfonate, toluenesulfonate, methanesulfonate, borate,phosphate, etc.

(b) A= NEYZ where Y is part of a heterocyclic ring containing thenitrogen atom, such as pyridine, alkyl pyrrolidine, etc. Z is the sameas in class 1(a).

(2) X=O or S and A is the anion of a strong acid, i.e.,

where V is SSO 050 etc. M is an alkali metal such as sodium, potassium,lithium, etc.

(3) X=O and A is a sulfonium salt, i.e.,

Rs A=% 2 where R R are saturated or unsaturated alkyl groups such asmethyl, ethyl, allyl, etc., and Z has the same meaning as in class 1(a).

Since A is a good leaving group for E type elimination and the hydrogensalpha to the sulfone are rendered acidic by the electron withdrawingcharacteristics of the sulfone group, these compounds readily revert tothe corresponding vinyl sulfone on the fabric when treated with alkalineagents, with concomitant reaction of the vinyl sulfone with thecellulosic hydroxyl groups to form a primary valence bond.

B leell 0N R-X--C5HlH-SOz(BH3HO-Cell These latent sulfone compounds havethe advantage over the corresponding vinyl sulfones in that they aresoluble or self-dispersing in aqueous systems, thereby eliminating theneed for extraneous dispersing or solubilizing agents which mightinterfere with the water repellency. They can, however, also be appliedto the fabrics from organic solvents such as dimethylformamide,dimethylsulfoxide, dimethylacetamide, etc., if so desired, with thealkali being applied at a later stage.

The following compounds are illustrative of the invention:fl-nonylphenoxyethyl vinyl sulfone, B-dodecyloxyethyl vinyl sulfone,B-tetradecyloxyethyl vinyl sulfone, B-n-hexadecyloxyethyl vinyl sulfone,fi-hexadecyloxyethyl vinyl sulfone (hexaethyl moiety contains chainbranching), B-octadecyloxyethyl vinyl sulfone, B-dodecylthioethyl vinylsulfone, fi-dodecylphenoxyethyl vinyl sulfone andN-methyl-N-dodecyl-fi-aminoethyl vinyl sulfone.

The new vinyl sulfone derivatives compounds may be prepared by reactionof a divinyl sulfone with an alcohol or mercaptan in the presence of acatalyst, or reaction of divinyl sulfone with a secondary amine at roomor an elevated temperature. Preferably, the temperature is about 200 C.and anhydrous conditions are used. Suitable catalysts are alkalinematerials such as alkali metals and their alkoxides. For example, sodiumethoxide, potassium methoxide, potassium ethoxide, sodium metal, lithiummetal and potassium metal may be used. It is also desirable to carry outthe reaction under an inert gas since this gives superior results,although this is not essential. This process is illustrated by thefollowing example, in which parts are by Weight.

EXAMPLE 1 Preparation of B-hexadecyloxyethyl vinyl sulfone A branchedchain hexadecyl alcohol (60.61 parts), divinyl sulfone (29.54 parts) and88 parts on anhydrous benzene were charged into a vessel equipped with astirrer, heating mantle, condenser and thermometer. Sodium methoxide(0.2 part) was added with stirring, the reaction mixture was stirred for13 minutes and an additional 0.1 part of sodium methoxide was added.After stirring for 12 minutes, the reaction mixture was refluxed for 203minutes followed by addition of 0.1 part of sodium methoxide. Thereaction mixture was then heated at reflux for 73 minutes, cooled, 0.5part of acetic acid added, and the benzene removed at reduced pressure.A yellow oil remained; weight, 91.1 part, percent OH, 0.82.

Other inert solvents may be used in place of benzene in this example,such as aromatic hydrocarbons. Toluene, xylene, etc. will givesatisfactory results.

These latent sulfone derivatives may be prepared by the following typesof reactions.

Compounds of the class 1a type (as designated above) can be prepared bytreating the ,G-substit-uted ethyl vinyl sulfone derivative with asecondary amine to form the ,B-aminoethyl derivative, followed byquaternization of the tertiary amine with typical alkylating agents suchas alkyl halides, sulfates, etc.

Compounds of the class 1b (as designated above) can be prepared by thesame technique as above, or by treating the ti-substituted ethyl vinylsulfone derivative with a mixture of the tertiary amine and in an acidsalt of the tertiary amine.

Compounds of the class 2 type (as designated above) for example when Ais SSO Na, can be prepared by treating the B-substituted ethyl vinylsulfone with sodium thiosulfate.

Compounds of the class 3 type can be prepared by treating theB-substituted ethyl vinyl sulfone with an alkyl mercaptan and analkaline catalyst to form the ,3'-thioether derivative, followed byalkylation of the S atom with typical alkylating agents such as alkylhalides (i.e., methyl iodide, etc.), alkali sulfates (i.e., dimethylsulfate), etc. to form the sulfonium salt.

EXAMPLE 2 Preparation offi-hexadeeyloxyethylsulfonylethylmethyldipropyl-ammonium methosulfatep-Hexadecyloxyethyl vinyl sulfone (7.2 parts) was dissolved in parts ofdioxane in a vessel equipped with a stirred, heating mantle, condenserand thermometer. Di-n-propylarnine (2 parts) was added and the mixtureheated slowly to reflux for 215 minutes. The solvent was then removed bydistillation under water vacuum.

Five parts of the above B-hexadecyloxyethyl-,3'-dipropylamino diethylsulfone and 40 parts of toluene were charged into a vessel and heated to100 C. A solution of 0.95 part of dimethyl sulfate dissolved in 10 partsof toluene was added slowly with stirring over a minute period and thereaction mixture was then maintained at 100 C. for an additional 60minutes. The toluene was removed by distillation and a tan low meltingsolid remained. This solid readily dispersed in water.

4 EXAMPLE 3 Preparation offl-hexadecyloxyethylsulfonylethylbutylmethyl-sulfonium methosulfate,B-Hexadecyloxyethyl vinyl sulfone (21.6 parts) was dissolved in partsof benzene in a vessel equipped with a stirrer, heating mantle,condenser and thermometer. n-Butyl mercaptan (6.0 parts) was addedfollowed by 0.05 part of sodium methoxide, and the mixture was stirredat 75 C. for one hour. The reaction mixture was then cooled to roomtemperature and neutralized with ethereal hydrogen chloride. A solutionof 2.6 parts of dimethyl sulfate dissolved in 30 parts of benzene wasadded slowly over a 60-minute period and the reaction mixture maintainedat reflux for 60 minutes. The benzene was then removed by distillationand a low melting solid remained which was readily dispersible in water.

EXAMPLE 4 Preparation of aqueous dispersion of sodiumfi-dodecylthioethylsulfonylethyl thiosulfate B-Dodecylthioethyl vinylsulfone (32 parts), sodium thiosulfate pentahydrate (50 parts) andsodium bicarbonate (8.4 parts) were heated with rapid stirring at 70 C.in 250 parts of dimethylacetamide for 30 minutes. Water parts) wasadded, the raction mixture stirred at 70 C. for 15 minutes and thenadded with stirring to 510 parts of water.

The procedure of Example 1 has also been employed in the production ofthe following compounds: p-dodecyloxyethyl vinyl sulfone,fl-tetradecyloxyethyl vinyl sulfone, ,B-hexadecyloxyethyl vinyl sulfone(straight chain), fi-octadecyloxyethyl vinyl sulfone, p-dodecylthioethylvinyl sulfone, fi-nonylphenoxyethyl vinyl sulfone,fi-dodecylphenoxyethyl vinyl sulfone.

Cellulosic textiles may be treated with these agents to cause theformation of a primary chemical bond by applying the treating agent tothe fabric and curing it by heating to an elevated temperature in thepresence of an acid binding agent. A reaction occurs between the vinylgroup of the sulfone and the hydroxyl function of the cellulosic toproduce the corresponding ether derivative of cellulose in accordancewith the following equation:

The hydrophobic sulfone is attached to the cellulosic by a primaryvalence bond. Hence, it is not removed by the solvents used fordry-cleaning or soap or detergent solutions normally employed forwashing in ordinary use.

The sulfones and latent sulfones may be dispersed or emulsified in anaqueous medium and the textile is immersed to soak up an adequatequantity. Aternatively, the treating agent may be dissolved in organicsolvent such as xylene, benzene, toluene, dimethyl sulfoxide, dimethylformamide, dimethyl acetamide, etc. in which the vinyl sulfonederivative or latent vinyl sulfone is soluble, but which do not containhydrogen sufliciently reactive that the solvent will react with thesulfone under alkaline conditions more readily than the cellulosictextile reacts with the sulfone. An acid binding agent may be dissolvedin the same aqeous medium or it may be applied by immersing the textilein a separate aqueous solution containing it before or after applyingthe sulfone treating agent. Preferably, when the organic solvent isused, the acid binding agent is in a separate solution in water, and thetextile is dried between soaking with the sulfone treating agent andwith the acid binding agent so that the repelling effect of wateragainst the organic solvent does not interfere with application of boththe acid binding agent and the sulfone treating agent to the textile.Suitable acid binding agents are the carbonates, hydroxides andbicarbonates of most metals such as alkali and alkaline earth metals.They include sodium carbonate, sodium hydroxide, potassium bicarbonate,potassium carbonate, and potassium hydroxide. They should have a pKbelow about 9.2.

The curing step is carried out at an elevated temperature, usually afterthe fabric has dried, of about 30 to 200 C. for about 24 hours to 30seconds. Generally, the treatments time varies inversely with thetemperature so that shorter times will be employed as the temperatureincreases.

The textiles to which the present treating agents may be applied arecellulosic textiles. This term refers to texiles composed of celluloseor modified cellulose, such as cotton, rayon, linen, etc., and mixturesthereof either with each other or non-cellulosics such as nylon(polyhexmethylene adipamide) or Perlon (polycaproamide) Dacron(polyethylene terephthalate) or Acrilan (an acrylic).

It has also been found that natural and synthetic waxes may beincorporated in the treating bath from which the vinyl sulfone isapplied to the textile and that a higher initial water repellency isobtained.

The following examples illustrate the use of the above sulfone compoundsin the treatment of cellulosic textiles. The spray test ratings wererated in accordance with AATCC Standard Test Method 22-52, which isdescribed on pages 164166 of volume 35 of the Technical Manual andYearbook of the American Association of Textile Chemists and Colorists.

EXAMPLE Application of fi-nonylphenoxyethyl vinyl sulfone to cotton Apiece of 80 x 80 cotton print fabric was immersed in a 2% aqueous sodiumhydroxide solution for 30 minutes, squeezed to 120% pickup and immersedin 4% xylene solution of B-nonylphenoxyethyl vinyl sulfone for minutes.The fabric was air dried, heated at 100-103 C. for 10 minutes, rinsedand washed (0.1% Na CO 0.1 nonionic surfactant prepared fromoxo-tridecyl alcohol and 7 moles of ethylene oxide). This fabric waswater repellent. Extraction of the fabric with boiling ethanol, carbontetrachloride and perchloroethylene did not reduce the water repellency.

EXAMPLE 6 Application of B-hexadecyloxyethyl vinyl sulfone to cottonB-Hexadecyloxyethyl vinyl sulfone (5.0 g.) was heated to 60 C. and addedwith rapid stirring to a solution of 2.0 g. of Duponol LS (sodium saltof sulfated oleyl alcohol) and 48 g. of water at 50 'C. The dispersionwas allowed to cool with stirring. A piece of 80 x 80 cotton printfabric was immersed in a bath containing a dispersion as above to whichwas added an equal volume of water as well as 1.25% sodium carbonate.The swatch was squeezed to 120% pickup,, air dried, heated at 150 C. for5 minutes, rinsed and washed. The fabric was water repellent and thisrepellency was not reduced by extraction with boiling ethanol, carbontetrachloride and perchloroethylene.

EXAMPLE 7 Application of B-hexadecyloxyethyl vinyl sulfone andmethylene-bis-stearamide to cotton A bath containing the following wasprepared:

Percent Dispersion containing 10% B-hexadecyloxyethyl vinyl sulfone(similar to that in Example '6) 45.0 Dispersion containingmethylene-bisstearamide 9.0 Sodium carbonate 2.2 Water 43.8

A piece of x 80 cotton print fabric was immersed,v

squeezed to pickup, air dried, heated 5 minutes at 150 C. and washedwith an aqueous bath containing 0.1% Na CO and 0.1% nonionic surfactantprepared from oxo-tridecyl alcohol and 7 moles of ethylene oxide. Thisfabric exhibited excellent water repellency (100 spray rating).

The following compounds have been applied to 80 x 80 cotton printfabrics:

B-dodecyloxyethyl vinyl sulfone (a) fl-tetradecyloxyethyl vinyl sulfone(a) fl-hexadecyloxyethyl vinyl sulfone (a) (b) B-octadecyloxyethyl vinylsulfone (a) (b) B-hexadecyloxyethyl vinyl sulfone (hexadecyl moietycontains chain branching) (b) fl-dodecylthioethyl vinyl sulfone (b)B-nonylphenoxyethyl vinyl sulfone (a) fi-dodecylphenoxyethyl vinylsulfone (a) N-methyl-N-dodecyl-fl-aminoethyl vinyl sulfone (a) (a)Application by xylene technique as in Example 5. (b) Application fromaqueous emulsion as in Exam plc 7.

EXAMPLE 8 Application of sodium S-dodecythioethylsulfonylethylthiosulfate to cotton A piece of 80 x 80 cotton print fabric wasimmersed in the dispersion described in Example 4, squeezed to 100%pickup, immersed in a 2% solution of potassium hydroxide, air dried, andheated at C. for 20 minutes. The fabric was then rinsed free of alkali,and after drying was water repellent. The water repellency remainedafter extraction of the fabric with boiling ethanol, carbontetrachloride and perchloroethylene EXAMPLE 9 Application of,B-hexadecyloxyethylsulfonylethylmethyldipropyl-ammonium methosulfate tocotton 5 Hexadecyloxyethylsulfonylethylmethyldipropylammoniummethosulfate (3 parts) was added to 96 parts of water at 40 C. and themixture stirred until homogeneous. A piece of 80 x 80 cotton printfabric was immersed in the dispersion, squeezed to 120% pickup, airdried, immersed in a 2% solution of sodium carbonate, air dried andheated at C. for 5 minutes. After rinsing free from alkali and thendrying the fabric was water repellent (50 spray rating) and the waterrepellency was unaffected by extraction of the fabric with boilingethanol, carbon tetrachloride and perchloroethylene.

The invention has been illustrated by specific examples, but it will beappreciated that various changes may be made in the nature of thetreating agents and in the manner in which they are applied withoutdeparting from the scope of the invention, as this is defined in theclaims.

What is claimed is:

1. A vinyl ethyl sulfone having the formula:

GUI-BUN 8. B-Hexadecyloxyethyl vinyl sulfone in which the CHARLES B.PARKER, Primary Examiner hexadecyl moiety contains alkyl chainbranching.

D. R. PHILLIPS, Asslstant Examiner References Cited UNITED STATESPATENTS 5 3,359,061 12/1967 Welch 260--607 XR 8-115.5, 116.2, 116;2528.7, 8.75; 260326.82, 567.6, 3,396,198 8/1968 Welch 260-607 294.8,583, 501.15, 567.6

